CN1253542A - Process and catalyst for preparing acetic acid by catalytic oxidation of ethane - Google Patents

Process and catalyst for preparing acetic acid by catalytic oxidation of ethane Download PDF

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Publication number
CN1253542A
CN1253542A CN98804455A CN98804455A CN1253542A CN 1253542 A CN1253542 A CN 1253542A CN 98804455 A CN98804455 A CN 98804455A CN 98804455 A CN98804455 A CN 98804455A CN 1253542 A CN1253542 A CN 1253542A
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oxygen
mixture
ethane
catalyst
gas
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CN1090605C (en
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H·博尔赫特
U·丁格第森
R·罗伊斯基
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Celanese AG
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Celanese AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6527—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
    • B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring

Abstract

A process is disclosed for selectively preparing acetic acid from a gaseous feed of ethane, ethylene or mixtures thereof, as well as oxygen, at an increased temperature, on a catalyst which contains the elements W, X, Y and Z in the gram-atom ratio a:b:c:d, associated with oxygen. In the formula WaXbYcZd (I), X stands for one or several elements selected from the group Pd, Pt, Ag and/or Au; Y stands for one or several elements selected from the group V, Nb, Cr, Mn, Fe, Sn, Sb, Cu, Zn, U, Ni and/or Bi; Z stands for one or several elements selected from the group Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ti, Zr, Hf, Ru, Os, Co, Rh, Ir, B, Al, Ga, In, Tl, Si, Ge, Pb, P, As and/or Te; a equals 1, b is a number higher than 0, c is a number higher than 0, and d is a number from 0 to 2. Also disclosed is said catalyst.

Description

The Catalyst And Method of preparing acetic acid by catalytic oxidation of ethane
The present invention relates to a kind of in the presence of tungsten-containing catalyst catalytic gas phase oxidation ethane and/or ethene select to prepare the method for acetate.
Be higher than under 500 ℃ the temperature, the ethane gas phase oxidation dehydrogenation becomes ethene to be disclosed in for example US-A-4250346, among US-A-4524236 and the US-A-4568790.A kind of catalyst composition is disclosed in US-A-4250346 in the application that ethane is changed on the ethene, this catalyst composition contains molybdenum, X and Y, its ratio is a: b: c, wherein: X is Cr, Mn, Nb, Ta, Ti, V and/or W, with Y be Bi, Ce, Co, Cu, Fe, K, Mg, Ni, P, Pb, Sb, Si, Sn, Tl and/or U, with a be 1, b is 0.05-1, c is 0-2.For Co, Ni and/or Fe, the total value of c must be less than 0.5.Reaction is preferably carried out adding under the condition of entry.Disclosed catalyzer also can be used for oxidation of ethane to acetic acid, and in this case, the efficient that changes into acetate is about 18%, and ethane conversion is 7.5%.
EP-A-0294845 discloses a kind of in the presence of a kind of catalyst mixture, and by the method for ethane, ethene or its mixture and oxygen selective production of acetic acid, wherein catalyst mixture contains: A.) general formula is Mo xV yOr Mo xV yZ yA kind of calcined catalyst, but one or more metals among Z Li, Na, Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg, Sc, Y, La, Ce, Al, TI, Ti, Zr, Hf, Pb, Nb, Ta, As, Sb, Bi, Cr, W, U, Te, Fe, Co and the Ni wherein, x is 0.5-0.9, y is 0.1-0.4, z is 0.001-1, and B.) a kind of ethylene hydration catalyzer and/or ethylene oxide catalyst.Second kind of catalyst component B be molecular sieve catalyst or contain the oxide catalyst of palladium particularly.Its highly selective can reach 27%, and ethane conversion is 7%.According to EP-A-0294845, have only the described catalyst mixture of use just can reach high ethane conversion, rather than use the single catalyst that only contains component A and B.
EP-A-0407091 discloses a kind of method for preparing the mixture of ethene and/or acetate.In this case, the gas of ethane and/or ethene and molecule-containing keto contacts with the catalyst composition that contains elements A, X and Y at elevated temperatures.Wherein A is Mo/Re/W, and X is Cr, Mn, Nb, Ta, Ti, V and/or W, and Y is Bi, Ce, Co, Cu, Fe, K, Mg, Ni, P, Pb, Sb, Si, Sn, Tl and/or U.Use this catalyzer, the highly selective of oxidation of ethane to acetic acid can be reached 78%.Formed other by product is carbonic acid gas, carbon monoxide and ethene.
Disclosed catalyzer all contains molybdenum as main ingredient in the described document.Yet the catalyzer that contains molybdenum has shortcoming, because under common reaction conditions, molybdenum forms the volatility molybdenum compound, has caused catalyst activity and optionally decline.
Above-mentioned document discloses without any one piece and has used the catalyzer that contains tungsten and precious metal that ethane and/or ethylene selectivity are oxidized to acetate.In addition, so far, the oxidation selectivity that prior art reached is also unsatisfactory.
Therefore purpose of the present invention provides a kind of with simple mode, the condition gentle as far as possible, the method that highly selective changes into ethane and/or ethylene oxy acetate.
Now find unexpectedly, by using combination to contain tungsten, precious metal (as Pd, Pt, Ag and Au) and one or more are selected from the catalyzer of the element of vanadium, niobium, tantalum, can under gentle relatively condition, ethane and/or ethylene oxy be changed into acetate with simple mode and highly selective.The volatility of tungsten oxide is more much lower than molybdenum oxide.Therefore, according to the present invention, replacing the activity of such catalysts of molybdenum and selectivity with tungsten is stable in long-term.
Therefore, the present invention relates to a kind of under the temperature that improves and optionally prepare the method for acetate on the tungsten-containing catalyst, by the phase feed of ethane, ethene or its mixture and oxygen or oxygen-containing gas, this catalyzer contains and oxygen bonded element W, X, Y and Z, and its grammeatom ratio is a: b: c: dW aX bY cZ d(I)
Wherein X is one or more elements that are selected from Pd, Pt, Ag and/or Au; Y is one or more elements that are selected from V, Nb, Cr, Mn, Fe, Sn, Sb, Cu, Zn, U, Ni and/or Bi; Z is one or more elements that are selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ti, Zr, Hf, Ru, Os, Co, Rh, Ir, B, Al, Ga, In, Tl, Si, Ge, Pb, P, As and/or Te, a is 1, b be one greater than 0 number, c is that a number and a d greater than 0 is the number of a 0-2.
X is preferably Pd, and Y is preferably V, Nb, Sb and/or Cu, and Z is preferably K, Ca, Si and/or P.
If X, Y are a plurality of different elements with Z, its index b, c and d can be different values.
The invention still further relates to a kind of catalyzer that contains with oxygen bonded element W, X, Y and Z, its grammeatom ratio is a: b: c: d.
Stoichiometry index b, c and d are preferably: b 0.0001-0.5c 0.1-1.0d 0.001-1.0.
In the methods of the invention, the value of b surpasses above-mentioned preferable range and may cause helping forming carbonic acid gas.In contrast, its content is lower than described preferable range, then observes preferential formation ethene.Preferred b value makes the present invention to carry out especially economically.
In another preferred version, except that elemental tungsten and palladium, catalyzer of the present invention can also contain and oxygen bonded vanadium, niobium and/or antimony and calcium.The grammeatom of element W: Pd: V: Nb: Sb: Ca is than a: b: c 1: c 2: c 3: d 1Be preferably: a (W)=1; B (Pd)=0.0001-0.5, particularly 0.0002-0.05; c 1(V)=0.1-1.0; c 2(Nb)=0.1-0.5; C 3(Sb)=0-0.5; d 1(Ca)=0-0.2.
The preferred especially in the present invention catalyzer example that uses is: W 1.00Pd 0.0005V 0.50Nb 0.12W 1.00Pd 0.0005V 0.75Nb 0.20W 1.00Pd 0.0004V 0.50Nb 0.20Cu 0.10P 0.05W 1.00Pd 0.0005V 0.50Nb 0.12Sb 0.10Ca 0.02W 1.00Pd 0.0004Au 0.0001V 0.75Nb 0.25Te 0.002W 1.00Pd 0.0005Ag 0.0001V 0.75Nb 0.12Si 0.01
Catalyzer of the present invention can be used from method preparation well known in the prior art.Can be from containing with the suspension of corresponding each the initial elementary composition of its ratio, particularly beginning preparation from the aqueous solution.
The parent material of each component of preparation catalyzer of the present invention removes the oxidation beyond the region of objective existence, and the preferably water soluble substance is as ammonium salt, nitrate, vitriol, halogenide, oxyhydroxide with can be the organic acid salt of corresponding oxide by thermal conversion.In order to mix these components, can prepare the aqueous solution or suspension with mixed-metal compounds.
The parent material of the tungsten that suggestion is used is corresponding tungstate, as ammonium tungstate, because it can have been bought from the market.
Resulting reaction mixture stirred 5 minutes to 5 hours down at 50-100 ℃.Then, remove and anhydrate, remaining catalyzer is at 50-150 ℃, and is particularly dry under 80-120 ℃ temperature.
When resulting catalyzer will be through roasting, suggestion 100 ℃-800 ℃, particularly 200-500 ℃ temperature with roasting exsiccant fine catalyst is being arranged under the condition that nitrogen, oxygen or oxygen-containing gas exist.Roasting time is preferably 2-24 hour.
Catalyzer can not use with carrier together, perhaps mixes or loads on a kind of carrier with a kind of carrier and use.Conventional solid support material is suitable, as porous silica, consolidation (geglutes) silicon-dioxide, diatomite, silica gel, porous or non-porous aluminas, titanium dioxide, zirconium dioxide, thorium dioxide, titanium dioxide lanthanum, magnesium oxide, calcium oxide, barium oxide, stannic oxide, cerium oxide, zinc oxide, boron oxide, boron nitride, norbide, borophosphoric acid, zirconium phosphate, silico-aluminate, silicon nitride or silicon carbide, also have glass fibre, metal oxide silk screen or wire cloth, or its corresponding material of integrating.
If catalyst cupport to carrier, can be finished by the catalyst component impregnated carrier with dissolved or suspension.Another may be, the solution or the suspension of catalyst component is mixed with the colloidal sol of solid support material, then spraying drying.In both cases, all then carry out described roasting.
The surface-area of preferred carrier materials is less than 100m 2/ g.Preferred solid support material is the silicon-dioxide and the aluminum oxide of low specific surface area.As multi-phase oxidation catalyst, catalyzer can use after being configured as rule or irregular load, or uses with powder type, or uses with above-mentioned form.
Reaction can be carried out in fluidized-bed or fixed-bed reactor.When using fluidized-bed, it is 10-200 μ m that catalyzer is crushed to particle diameter usually, or is prepared by spraying drying.
Contain that ethane/or the gas raw material of ethene can scrubbed gas or be input in the reactor with the form of the mixture of one or more other gases.The suitable example of these additional gas or carrier gas is nitrogen, methane, carbon monoxide, carbonic acid gas, air and or steam.The gas of molecule-containing keto can be the gas that air or molecule keto concentration are higher or lower than air, as pure oxygen.The ratio of steam can be in the 0-50% volume range.Higher vapor concentration may pollute resulting acetate, owing to the reason of technology can make cost unnecessarily raise, but is possible technically.The molar ratio of ethane/ethylene and oxygen is preferably between 1: 1 and 10: 1, preferably between 2: 1 and 8: 1.High oxygen concentration is preferred, because can obtain high ethane conversion, so the productive rate height of acetate.The gas that preferably adds oxygen or molecule-containing keto in the limits of explosion under the reaction conditions is because simplified the implementation process of method like this.Yet, also ethane/ethylene/oxygen mixture can be adjusted in the limits of explosion.
Reaction is preferably carried out under 200-400 ℃ temperature normally at 200-500 ℃.Pressure can be normal pressure or surpass a normal atmosphere, as cling to preferred 1-30 crust at 1-50.
Reaction can be carried out in fixed bed or fluidized-bed reactor.Before the gas of input oxygen or molecule-containing keto, ethane rare gas element first usually and as nitrogen or steam mixes.With before catalyzer contacts, mixed gas is preheating to temperature of reaction in the preheating zone usually.Usually by condensation, from the gas that leaves reactor, remove acetate.Other gas Returning reactor inlet is at gas, ethane and/or the ethene of ingress metering oxygen or molecule-containing keto.
Embodiment
Catalyst composition among the embodiment is with the expression of relative atom ratio.
Preparation of catalysts:
Catalyzer (I):
Preparation has the catalyzer of following composition:
W 1.00Pd 0.0005V 0.25Nb 0.12
Under 90 ℃, the 100g ammonium metawolframate is suspended in the 500ml water.Under 90 ℃, in this mixture, drip the solution of 11.2g ammonium meta-vanadate in 250ml water.Mixture after the merging stirred 15 minutes down at 90 ℃.Then, under 90 ℃, the solution of Dropwise 35 .7g niobium oxalate in 400ml water in this mixture.Mixture after the merging stirred 15 minutes down at 90 ℃.At last, add the solution of 0.043g acid chloride in 50ml acetone in resulting mixture, mixture stirred 15 minutes down at 90 ℃.Evaporate moisture then, the resistates after the evaporation is 120 ℃ of following dried overnight.(part＜2mm), the rate of heating with 2 ℃ of per minutes is heated to 400 ℃ to sieve to broken solid in airflow again.Kept this temperature 4 hours.Turn off airflow, raw material is cooled off gradually.With break-up of catalyst and extruding (2 tons of pressure) and screening, sieve part of acquisition is between 0.35-0.7mm.
Catalyzer (II):
W 1.00Pd 0.0005V 0.50Nb 0.12
Under 90 ℃, the 100g ammonium metawolframate is suspended in the 500ml water.Under 90 ℃, in this mixture, drip the solution of 22.4g ammonium meta-vanadate in 250ml water.Mixture after the merging stirred 15 minutes down at 90 ℃.Then, under 90 ℃, the solution of Dropwise 35 .7g niobium oxalate in 400ml water in this mixture.Mixture after the merging stirred 15 minutes down at 90 ℃.At last, add the solution of 0.043g acid chloride in 50ml acetone in resulting mixture, mixture stirred 15 minutes down at 90 ℃.Evaporate moisture then, the resistates after the evaporation is 120 ℃ of following dried overnight.(part＜2mm), the rate of heating with 2 ℃ of per minutes is heated to 400 ℃ to sieve to broken solid in airflow again.Kept this temperature 4 hours.Turn off airflow, raw material is cooled off gradually.With break-up of catalyst and extruding (2 tons of pressure) and screening, sieve part of acquisition is between 0.35-0.7mm.
Catalyzer (III):
W 1.00Pd 0.0005V 1.00Nb 0.12
Under 90 ℃, the 100g ammonium metawolframate is suspended in the 500ml water.Under 90 ℃, in this mixture, drip the solution of 44.4g ammonium meta-vanadate in 250ml water.Mixture after the merging stirred 15 minutes down at 90 ℃.Then, under 90 ℃, the solution of Dropwise 35 .7g niobium oxalate in 400ml water in this mixture.Mixture after the merging stirred 15 minutes down at 90 ℃.At last, add the solution of 0.043g acid chloride in 50ml acetone in resulting mixture, mixture stirred 15 minutes down at 90 ℃.Evaporate moisture then, the resistates after the evaporation is 120 ℃ of following dried overnight.(part＜2mm), the rate of heating with 2 ℃ of per minutes is heated to 400 ℃ to sieve to broken solid in airflow again.Kept this temperature 4 hours.Turn off airflow, raw material is cooled off gradually.With break-up of catalyst and extruding (2 tons of pressure) and screening, sieve part of acquisition is between 0.35-0.7mm.
Catalyzer (IV):
W 1.00Pd 0.0005V 0.50Nb 0.12Sb 0.10Ca 0.02
Under 90 ℃, the 100g ammonium metawolframate is suspended in the 500ml water.Under 90 ℃, in this mixture, drip the solution of 22.4g ammonium meta-vanadate in 250ml water.Mixture after the merging stirred 15 minutes down at 90 ℃.Then, under 90 ℃, Dropwise 35 .7g niobium oxalate, 9.7g antimony oxalate, the solution of 1.8g nitrocalcite in 400ml water in this mixture.Mixture after the merging stirred 15 minutes down at 90 ℃.At last, add the solution of 0.043g acid chloride in 50ml acetone in resulting mixture, mixture stirred 15 minutes down at 90 ℃.Evaporate moisture then, the resistates after the evaporation is 120 ℃ of following dried overnight.(part＜2mm), the rate of heating with 2 ℃ of per minutes is heated to 400 ℃ to sieve to broken solid in airflow again.Kept this temperature 4 hours.Turn off airflow, raw material is cooled off gradually.With break-up of catalyst and extruding (2 tons of pressure) and screening, sieve part of acquisition is between 0.35-0.7mm.
Catalyzer (V):
W 1.00Pd 0.0005Ag 0.0001V 0.75Nb 0.12Si 0.01
Under 90 ℃, the 100g ammonium metawolframate is suspended in the 500ml water.Under 90 ℃, in this mixture, drip the solution of 33.6g ammonium meta-vanadate in 250ml water.Mixture after the merging stirred 15 minutes down at 90 ℃.Then, under 90 ℃, Dropwise 35 .7g niobium oxalate, 0.01g Silver Nitrate, the suspension of 0.23g diatomite in 400ml water in this mixture.Mixture after the merging stirred 15 minutes down at 90 ℃.At last, add the solution of 0.43g acid chloride in 50ml acetone in resulting mixture, mixture stirred 15 minutes down at 90 ℃.Evaporate moisture then, the resistates after the evaporation is 120 ℃ of following dried overnight.(part＜2mm), the rate of heating with 2 ℃ of per minutes is heated to 400 ℃ to sieve to broken solid in airflow again.Kept this temperature 4 hours.Turn off airflow, raw material is cooled off gradually.With break-up of catalyst and extruding (2 tons of pressure) and screening, sieve part of acquisition is between 0.35-0.7mm.
Catalyzer (VI):
W 1.00Pd 0.0004V 0.50Nb 0.2Cu 0.10P 0.05
Under 90 ℃, the 100g ammonium metawolframate is suspended in the 500ml water.Under 90 ℃, in this mixture, drip the solution of 22.4g ammonium meta-vanadate in 250ml water.Mixture after the merging stirred 15 minutes down at 90 ℃.Then, under 90 ℃, Dropwise 5 9.5g niobium oxalate, 8.91g cupric nitrate, the suspension of 1.6g phosphoric acid (85%) in 400ml water in this mixture.Mixture after the merging stirred 15 minutes down at 90 ℃.At last, add the solution of 0.034g acid chloride in 50ml acetone in resulting mixture, mixture stirred 15 minutes down at 90 ℃.Evaporate moisture then, the resistates after the evaporation is 120 ℃ of following dried overnight.(part＜2mm), the rate of heating with 2 ℃ of per minutes is heated to 400 ℃ to sieve to broken solid in airflow again.Kept this temperature 4 hours.Turn off airflow, raw material is cooled off gradually.With break-up of catalyst and extruding (2 tons of pressure) and screening, sieve part of acquisition is between 0.35-0.7mm.
Catalyzer (VII):
W 1.00Pd 0.0003Au 0.0001V 0.75Nb 0.25Te 0.002
Under 90 ℃, the 100g ammonium metawolframate is suspended in the 500ml water.Under 90 ℃, in this mixture, drip the solution of 22.4g ammonium meta-vanadate in 250ml water.Mixture after the merging stirred 15 minutes down at 90 ℃.Then, under 90 ℃, in this mixture, drip 74.4g niobium oxalate, 0.015g tetra chlorauric acid, the solution of 0.18g telluric acid in 400ml water.Mixture after the merging stirred 15 minutes down at 90 ℃.At last, add the solution of 0.026g acid chloride in 50ml acetone in resulting mixture, mixture stirred 15 minutes down at 90 ℃.Evaporate moisture then, the resistates after the evaporation is 120 ℃ of following dried overnight.(part＜2mm), the rate of heating with 2 ℃ of per minutes is heated to 400 ℃ to sieve to broken solid in airflow again.Kept this temperature 4 hours.Turn off airflow, raw material is cooled off gradually.With break-up of catalyst and extruding (2 tons of pressure) and screening, sieve part of acquisition is between 0.35-0.7mm.
The testing method of catalyzer
The 10ml catalyzer is joined in the stainless steel reactor that internal diameter is 10mm.Catalyzer is heated to 250 ℃ in airflow.Utilize pressure controller to regulate pressure then.Required ethane/oxygen/nitrogen mixture and water metering input evaporating area, water here is evaporated and mixes with gas.Temperature of reaction is measured with the thermoelectric converter in the catalyst bed.With online gas chromatographic analysis reactant gases.
Following term among the embodiment is definition like this:
Ethane conversion (%)=
100×([CO]/2+[CO 2]/2+[C 2H 4]+[CH 3COOH])/([ CO]/2+[CO 2]/2+[C 2H 4]+[C 2H 6]+[CH 3COOH])
Ethylene selectivity (%)=
100×([C 2H 4])/([CO]/2+[CO 2]/2+[C 2H 4]+[CH 3COOH])
Acetic acid selectivity (%)=
100×([CH 3COOH])/([CO]/2+[CO 2]/2+[C 2H 4]+[CH 3COOH])
Wherein
[]=volumetric molar concentration % and
[C 2H 6The concentration of]=unreacted ethane.
The residence time is defined as:
The volume (ml) of t (s)=catalyzer/under reaction conditions, the flow through volumetric flow rate of reactor
(ml/s)。
Reaction process:
The unstripped gas of reactor is made up of the ethane of 40% volume, the oxygen of 8% volume, the nitrogen of 32% volume and the steam of 20% volume.Reaction conditions and the results are shown in the following table.
Embodiment Catalyzer Temperature (℃) Pressure (crust) The residence time (second) Ethane conversion (%) Acetic acid selectivity (%) Ethylene selectivity (%) CO+CO 2Selectivity (%)
????1 ????I ????280 ????15 ????30 ????7 ????57 ????2 ????41
????2 ????I ????290 ????15 ????30 ????8 ????56 ????3 ????41
????3 ????I ????300 ????15 ????30 ????9 ????56 ????3 ????41
????4 ????II ????260 ????15 ????30 ????8 ????76 ????1 ????23
????5 ????II ????280 ????15 ????30 ????10 ????74 ????2 ????24
????6 ????II ????280 ????15 ????15 ????10 ????75 ????3 ????22
????7 ????III ????260 ????15 ????30 ????9 ????81 ????0 ????19
????8 ????III ????270 ????15 ????30 ????11 ????79 ????0 ????21
????9 ????III ????280 ????15 ????30 ????11 ????78 ????1 ????21
????10 ????IV ????260 ????15 ????30 ????7 ????80 ????1 ????19
????11 ????IV ????280 ????15 ????30 ????10 ????75 ????4 ????21
????12 ????V ????250 ????15 ????25 ????8 ????78 ????1 ????21
????13 ????V ????260 ????15 ????20 ????9 ????77 ????3 ????20
????14 ????VI ????250 ????15 ????20 ????10 ????80 ????1 ????19
????15 ????VII ????280 ????15 ????30 ????8 ????77 ????2 ????21

Claims (13)

  1. One kind under the temperature that improves, on tungsten-containing catalyst, optionally prepare the method for acetate by the gas raw material of ethane, ethene or its mixture and oxygen or oxygen-containing gas, wherein, tungsten-containing catalyst contains and oxygen bonded element W, X, Y and Z, and its grammeatom ratio is a: b: c: d
    W aX bY cZ d(I) wherein X is one or more elements that are selected from Pd, Pt, Ag and/or Au; Y is one or more elements that are selected from V, Nb, Cr, Mn, Fe, Sn, Sb, Cu, Zn, U, Ni and/or Bi; Z is one or more elements that are selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ti, Zr, Hf, Ru, Os, Co, Rh, Ir, B, Al, Ga, In, Tl, Si, Ge, Pb, P, As and/or Te, a is 1, b be one greater than 0 number, c is that a number and a d greater than 0 is the number of a 0-2.
  2. 2. the method for claim 1 is characterized in that, X, Y and Z are generally multiple element, for different elements, and the desirable different value of its index b, c and d.
  3. 3. claim 1 and/or 2 method is characterized in that temperature of reaction is 200-500 ℃, preferred 200-400 ℃.
  4. 4. at least one method among the claim 1-3 is characterized in that, reactor pressure is the 1-50 crust, is preferably the 1-30 crust.
  5. 5. at least one method among the claim 1-4 is characterized in that, b is 0.0001-0.5.
  6. 6. at least one method among the claim 1-5 is characterized in that, c is 0.1-1.0.
  7. 7. at least one method among the claim 1-6 is characterized in that, d is 0-1.0.
  8. 8. at least one method among the claim 1-7 is characterized in that, ethane is with at least a other gas input reactor.
  9. 9. the method for claim 8 is characterized in that, other gas is nitrogen, oxygen, methane, carbon monoxide, carbonic acid gas, ethene and/or steam.
  10. 10. at least one method among the claim 1-9 is characterized in that, catalyzer comprise at least a with the following composition of oxygen bonded: W 1.00Pd 0.0005V 0.50Nb 0.12W 1.00Pd 0.0005V 0.75Nb 0.20W 1.00Pd 0.0004V 0.50Nb 0.20Cu 0.10P 0.05W 1.00Pd 0.0005V 0.50Nb 0.12Sb 0.10Ca 0.02W 1.00Pd 0.0004Au 0.0001V 0.75Nb 0.25Te 0.002W 1.00Pd 0.0005Ag 00001V 0.75Nb 0.12Si 0.01
  11. 11. at least one method is characterized in that among the claim 1-10, catalyzer mixes with solid support material or is fixed on the solid support material.
  12. 12. at least one method is characterized in that among the claim 1-11, ethane/ethylene to the molar ratio of oxygen between 1: 1 to 10: 1, preferably between 2: 1 to 8: 1.
  13. 13. a tungsten-containing catalyst that is used for oxygen selective ground ethyl oxide, ethene or its mixture, it contains and oxygen bonded element W, X, Y and Z, and its grammeatom ratio is a: b: c: d
    W aX bY cZ d(I) wherein X is one or more elements that are selected from Pd, Pt, Ag and/or Au; Y is one or more elements that are selected from V, Nb, Cr, Mn, Fe, Sn, Sb, Cu, Zn, U, Ni and/or Bi; Z is one or more elements that are selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ti, Zr, Hf, Ru, Os, Co, Rh, Ir, B, Al, Ga, In, Tl, Si, Ge, Pb, P, As and/or Te, a is 1, b be one greater than 0 number, c is that a number and a d greater than 0 is the number of a 0-2.
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GB9907704D0 (en) 1999-04-01 1999-05-26 Bp Chem Int Ltd Catalyst and process utilising the catalyst
JP4486751B2 (en) * 1999-06-25 2010-06-23 サウディ ベーシック インダストリーズ コーポレイション Catalyst system for one-stage gas phase production of acetic acid from ethylene
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JP4809532B2 (en) * 1999-11-15 2011-11-09 サウディ ベーシック インダストリーズ コーポレイション Catalyst for catalytic oxidation of propane to acrylic acid, its production and use
US6693059B2 (en) * 2000-02-09 2004-02-17 Rohm And Haas Company Process for preparing a catalyst and catalytic oxidation therewith
US6531631B1 (en) 2000-04-28 2003-03-11 Saudi Basic Industries Corporation Oxidation of ethane to acetic acid and ethylene using molybdenum and vanadium based catalysts
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